Amines are an important functional group present in a variety of biologically relevant molecules; however, examples of transition metal-mediated terminal C-H oxidation of amines remain scarce. Two of the major challenges associated with the functionalization of amines are: (1) the Lewis basic nitrogen can bind to and deactivate metal catalysts and (2) the C-H bonds α to nitrogen are highly activated towards oxidation. We have developed a new approach toward the terminal C(sp3)-H functionalization of aliphatic amines. We utilize the inherent selectivity associated with Pt-catalyzed C-H oxygenation of alkanes to perform selective oxidation of aliphatic amines under acidic conditions. The in situ formation of an ammonium salt serves to prevent binding to Pt, as well as to deactivate the C-H bonds proximal to the nitrogen center towards functionalization. This strategy has allowed us to achieve selective terminal functionalization of a variety of primary, secondary, and tertiary amines with low Pt loadings and high TONs. In addition, we have also been able to utilize CuCl2 as an inexpensive stoichiometric oxidant.

Platinum-catalyzed, terminal selective C(sp3)-H oxidation of aliphatic amines

251st National Meeting (2016)

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